Ester of polycarboxylic acids



Patented 11, 1934 UNITED STATES PATENT ornca 1m )8!!! OI W ACID! vIbeneser Emmet Md. Baltimore, Id, and George L. Bohwarh. Wilmington.DeL, assigncn tolhdlrontdeflemourl acompanmwilminst m Del -a corporationof Dehware No Drawing- Application '5. 1081. Serlal No. 518.718

11 claims- (Cl. 260-108) This invention relates to compositionscontainplisbcd by a selection oi two or more alcohols inganarylalkyloraryl arylesterof apolycarthat.whencombinedinthesamechemicalcomacid and, more. ly. cellulose pound. give low meltingcompounds. or, as ester compositions, and still more particularly.stated otherwise, by the use of an aryl alcohol to celluloa estercompositions containing bensyl neutralise one carbonyl group and analkyl alcoethyl phthalate.

In the practical application of dissolved cellulose and soluble celluloucompounds. including cellulose esters, to the various arts andmanufacture, such as the production of films. varnishes, filaments,plastic masses, etc.. it is customary to blend or mix or otherwise addto the cellulose ester, or to its solution, certain non-cellulosicmaterials commonly termed softeners, camphor substitutes or the like.such additions being made for the purpose of impartins to the compoundssome desired properties, such as noninfiamm biiity. plasticity underheat, flexibility.v etc. These softeners. camphor substitutes and thelike, which we shall hereinafter for convenience designate as"modifiers", function in manydiiferent ways in cellulosic combinations;and the properties which they impart to the prodand are determined byboth the physical and the chemical properties of the particular modifierused. For example. if a modifier is non-inflammable, it will impart thisprop r tothecellulosetoadegreewhich isofcoursedependent upon thecharacter of the modifier and the proportion added; if the modifier isrelatively non-volatile its effect will be more permanent thanthatofamore volatilemodifier; ifthe modiher is a solvent under suitableconditions for the cellulou material. it will as a rule impart greaterflexibility than if it is a non-solvent; and particularly, modifierswhich are liquid at normal temperatures will. other things being equal.impart greater fiexibilitythanthosewhicharesolid at normal temperatures.

This invention therefore comprises the use of mixed esters havingextremely low volatility and range as modifiers for cellulose nitratecompositions modified pliable, extremely tough,

cover a range wide enough to produce hard, tough films with maflexibility but low stretch, and soft pliable films with high stretchwithout lowering the transparency and homogeneity of the product. Theproducts are not influenced much by temperature variations and are'notbrittle when cold. The esters do not exude from thesm'faceathightemperaturesorcrystalliseonthe surface atlowtemperatures.Thisisawomcellulose or its,

hol to neutralize another carboxyl group of a poly boxylic acid.compounds are obtained that have greater temperature spans between theirmelting points and boiling points than when only one alcohol is used.when acids are used that contain more than two carboxyl groups theintroduction of a third or fourth alcohol can be accomplished sometimeswith beneficial results.

The esters that we have found more suitable as modifiers than mostsubstances heretofore proposed for this purpose include the aryl alkylesters of phthalic, tartaric, are not limited, however, to these estersand may form mixed esters by various combinations of alcohols, such as:

Phenol, CsKsOH.

Tolyl (nlyl) alcohol. Beta phenyl-ethyl alcohol, CWEI H, Phenyl-methylalcohol, CsHsCHOH-Cfls, cinnamyl alcohol, CsKsCH=CH-CH:OH, Cresol,CHflsHAOH,

Methyl alcohol. CHsOH.

Ethyl alcohol. ClHtOH.

Propyl alcohol. CsH'lOH.

Butyl alcohol. 041E108.

Amyl alcohol, CsHnOH.

with various acids. such as:

v Phthalic, CsH4(COOH) a.

Dihydroxy terephthalic, CeHs(OH)s(COOH) s, Phenyl malonic.COOHCH(CsI-Is) .COOH, Tartaric. COCK-CHOH-CHOH-COOH. Pyromellitic.CsH:(COOH)4. Citric, OOOH-CHsC(OH) (00019-05:- COOK.

' Benzwl butvl phtholate and citric acids. We

2boilingpointotbutylalcoholtoremoveitbydistillatlonasrapidlyasitistormedwiththeresultthat the reaction Proceeds practically to com! 'pletion as indicated bythe iollowina equation:

' ooodh +Oomon 000m.

meals m that line content and has a 'lhetollowingweilhtsoi'materialsareusedror Marathi: v

the

Pourads Dibutylphthaiate 9 .8

alcohoL ad 'the liquid is held at 50' C. when the reaction is completethe dibutyl m the an it la of mercury w e rapidly 40 when the WW1alcohol beslnstotol h peratureisaraduallyraised 15C.andwen no more butylalcohol dlstiis the sodium salt drated by heating at 100 C. under Thefinished product is a neutral, clear, light yelloworbrownoilthatistreeoit. It

possesse a faint odor oi' benayl alcohol. The as- 9 for contentcalculated as bcnzyl hutyl phthalate is about 08%.

Benny! butyl bhthalate is chemically inert in its action on a pyroxyllnfilm.

55 very active llisments such as zinc oxide without causing unduedeterioration of the pyroxylin such andisd hy- Mom-Q the 'l'osneoflreduced pres-.

It can be used with P artsby Pyroxylin 12.05% nitrogen Dry lamentVolatile solventr l -i -100 The lower limits of benzyl butyl phthalate nthis kind are power of the mixture.

Although the neutral phthalates of the various isomeric butyl alcoholsas a Benzyl butul tar-trots When it is desired to utilize hem! oftartaric acid.

phthalate, the only change the use 01' the the following equation:

(Oomom mm omom-oooolm cumin-000mm 1m. wt. m we omom-ooooE-Q omom-oooolmThe following weights of for the preparation 01' benzyl onion smaterials are used butyl tartrate:

Dibutyl tartrate -e 01.2

Benzyl alcohol-.. 80

Metallic sodium .5

Benzyl ethill phthalate One hundred and eight grams (1 mol) oi benzylalcohol (commercial grade only a small amount of halogen by Beilstclntest) was placed in a oneliter distilling flask. The flask was mm.otmercury The temperature was mm slowly to as" while p per properPhenol-ethyl eflwl mum Esactlythesameprocedurewasusedtow' parephenvl-ethyl ethyl phthalate as was given for bensyl ethyl phthalate.The quantities were as follows:

m g. (1 mol) of beta phenyl-etbyl alcohol 1.3 g. -(.iiiiil moi) sodiummetal same manner asjustdescrihedandwere forsixhours.Attheendolthisperlodthemixture had the appearance of apple sauce.alcoholthatwascollectedweighedflg.against thetheoreticalrecoveryofaog.After withwateranddryinginvacmrmatldd'QtMproductwasaiightlemonyellowtransparcntoil. The yieldwasl'n g.or 91%ofthe theoretical.

(om-ominous) mun our-000cm OM00 Ba mavens. I

Cir-0000 no -cooon.cn.0.m+c.mon

ethyl) ethyl citrate. instead of ethyl diet-M1 citrate as above.

e,wheredesired.onemoiofbutyi alcoholandonemolofphenyl-ethyl alcohol canbeaddedatthesametimeand-twomolsofethylalcoholaredisplacedwiththeformationofan ester which contains an ethyl. ahutyl, and a phenyl-ethyl group. I

Bysuhstitutingmolweightsofthevariousalcoholshereinlisted,andotheralcoholsofthesemalargelistofotherestersispreparedthat are excellent modifiers ofcellulose nitrate. some of these substances are:

Bensyl methyl phthalate Benayl ethyl dihydroxy terephthalate Benayiethyl phenyl-malonate Benayl ethyl tartrate Benayl ethyl succinateBenayl ethyl citrate- Bennl ethyl pyromellitate Phenyl-ethyl cresylphthalate Cinnamyl ethyl phthalate Phenyl-methyl ethyl phthalate Bensyltolyl (niyl) phthalate As indicated above. we prefer to produce thesemodiilers by the catalytic aicoholysis of the simpleneutralesters'withoneofthealcohols thatisto he added to the finalproduct in the presence of the sodium alcoholate of the higher boilinlalcohol which is to he introduced although directesteriilcationisinsomecasespractlcahle. Inthismanner the primaryesterincation to neutralization of theacidisaccomplishedwithonealeohol,usually.

the lower'boiling alcohol. One or more of these alcoholic groups is thenremoved by the second reaction. which is the aicoholysis reaction. by

conh-ollingtheamountofthehiaherboilng alcohol that is added to thereaction mixture. This in an equilibrium reaction in which advantage istaken of the lower boiling alcohol, which hasbeenusedtoneutralisetheacld.toremove ithy distillation as rapidly as itis formed'with the result that the reaction proceeds practically tocompletion. This method of introducing a high boilof ethyl alcohol aredisplaced. fol-min: di(phenyling alcohol into a compound has certainadvantagessuchasthegreaterpurityoftheproducts obtained.lower temperatureof reaction. and ease with which this type of esteriflcation occurs,especially with the higher alcohols. This conversion at lowtemperatures-is of special importance withthehigheralcoholasuch asbenzylandtolylalcoholswhicharereadilyconvertedto the ethers at temperaturesrequired for direct esteriflcationintheofacatalyst, such assulfuricacid.

The catalyst forthe aicoholysis reaction isformedhyaddingonemolofsodiummetaltoone moi of the anhydrous alcohol. andpreferably heating tofacilitate the reaction, but controllingthetemperaturesoitdoesnotexceedw" C. Thehighhoilingalcoholsarereadilyobtainedinthe anhydrous form by simpledistillation of a foreshotwhichcontainsallofthewater. Inthesamemannertheneutralesterofthelower boillngalcoholisdAnhydrousconditions are essential for high yields but the method ofdehydrating the reagents as shown is relatively simple and alsoeconomical.

We prefer to use these products in the washed, undistilled condition asmodifiers for cellulou nitrates. although for certain special uses thet.afractlosiamdprd uctsmayheusedwithadvan-Thesemodiflersofcellulosenitrateareused .15 terms as "aryP andaryl-alkyl" to be interdrocerbon m1 hy mixed tho-Dhthalate. is

I 85 We claim: GEORGE L. SCHWARTZ. 35

with cellulose nitrate containing 8.7% drocarbon aryl ethyl mixed esterof a polycarmen to 12.0% nitrogen and are especially boxlic acid whichcontains no unsaturated ah I 'l h d'terln ry isusedherein todesiznateany 2. A composition of matter comprising a hyl a group thatcontains an aromatic group (except droearbon aryl ethyl mixed eeterof adicarboxylic completely hydrozenated aromatic :roups) such acid whichcontains no unsaturated alkyl group. as phenyl. benzyl or phthalate.Some authori- 3. A composition of matter comprising a hytics, however;use the term "aryl-alkyl" to desig- (13008130118351 ethyl mixed ester ofa dicarboxyllc nate roducts containing abenzyl group which aroma c 10 isforiiied by the substitution of a phenyl noun 4. A omposition of mattercomp rlslnli a 2 10 for a hydrogen of an alkyl group. In order that c ron W hyl mix d cr 1' D all the terminology of the present applicationmay be 5. A composition of matter comprising benzyl flexible enough tocoincide with both types of ethyl ortho-Ph hal8 etcrlninoloa'y,applicants wish their use of such 6- A.c0lnp0sltion of matter comprisinga hyn o th l th ir t r- "I. Benzyl-ethyl ortho-phthalate having a boil-3:21 :3 l na :0 l ncide :i tll that used'by Others 8 Point of under in mP r in referring to the same materials. pp x mately 3 mm. of me The useof the mixed esters disclosed herein is A mposition matter mprising ahis;- 20 not llmted to cellulose nitrate composltons as drocflrbon 7mixed ester tof a polycai'bon o no they are also useful in connectionwith other M d which contains 110 111188 m d ba-damsel: cellulosederivatives. such as celluloseacetate and 1d ydrocarbon aryl mixedclatter beingthylec l ethyl cellulose. 1 t g l :2: gl lmcmlsts an e aryThisa licationisinpartacontinuatono 25 our applll ltlon Serial NO.41,409, flled- Jilly 8, A composition of sgid 823d 25 1925, for"Softeners for pyroxylins, in which m 7 mixed 0! P ed-nom celluloseester compositions containing .benzyl hydrocarbon 7 2211 fis y OM butylphthalate are claimed specifically. the n w which g 0 r: err

As many apparently wid ly diiferentembodland W er mm be 1 so so ments ofthis invention may be mad;1 g o m e mine new i the int and scope ereo mI g fi b e u ndxood 1 we do not limit ourselves A composition of mattercomprising nzrl to the specific embodiments thereof except as Phtmlate-4 v defined in the appended patent claims. EBENEZER. REID.

l. A composition of matter comprising a by- I Certificate of CorrectionPatent No. 1,984,283. v I

' EBENEZER EMMET REID ET AL.

It is hereby certified that errors appear in tHeIPrinted specificationof theabove December 11, 1934.

numbered patent re uu-l correction as follow age 1, second column, line37, for the period before 0O second occurrence insert a dash; age 3,first column, e 48, strike out-last line of formula and insert instead(6 11030005 and page 4, second column, line 2, claim 1, for the syllableboxlic read bozyl'ic; and that the said Letters Patent should be readwith these corrections therein that the same may conform to the recordof the case in the Patent Ofiice.

Signed andsealed this 5th day of March, A. B21935.

- I LESLIE FRAZER, Acting Commissioner qfPatente.

.15 terms as "aryP and aryl-alkyl" to be interdrocerbon m1 hy mixedtho-Dhthalate. is

I 85 We claim: GEORGE L. SCHWARTZ. 35

with cellulose nitrate containing 8.7% drocarbon aryl ethyl mixed esterof a polycarmen to 12.0% nitrogen and are especially boxlic acid whichcontains no unsaturated ah I 'l h d'terln ry isusedherein todesiznateany 2. A composition of matter comprising a hyl a group thatcontains an aromatic group (except droearbon aryl ethyl mixed eeterof adicarboxylic completely hydrozenated aromatic :roups) such acid whichcontains no unsaturated alkyl group. as phenyl. benzyl or phthalate.Some authori- 3. A composition of matter comprising a hytics, however;use the term "aryl-alkyl" to desig- (13008130118351 ethyl mixed ester ofa dicarboxyllc nate roducts containing abenzyl group which aroma c 10 isforiiied by the substitution of a phenyl noun 4. A omposition of mattercomp rlslnli a 2 10 for a hydrogen of an alkyl group. In order that c ron W hyl mix d cr 1' D all the terminology of the present applicationmay be 5. A composition of matter comprising benzyl flexible enough tocoincide with both types of ethyl ortho-Ph hal8 etcrlninoloa'y,applicants wish their use of such 6- A.c0lnp0sltion of matter comprisinga hyn o th l th ir t r- "I. Benzyl-ethyl ortho-phthalate having a boil-3:21 :3 l na :0 l ncide :i tll that used'by Others 8 Point of under in mP r in referring to the same materials. pp x mately 3 mm. of me The useof the mixed esters disclosed herein is A mposition matter mprising ahis;- 20 not llmted to cellulose nitrate composltons as drocflrbon 7mixed ester tof a polycai'bon o no they are also useful in connectionwith other M d which contains 110 111188 m d ba-damsel: cellulosederivatives. such as celluloseacetate and 1d ydrocarbon aryl mixedclatter beingthylec l ethyl cellulose. 1 t g l :2: gl lmcmlsts an e aryThisa licationisinpartacontinuatono 25 our applll ltlon Serial NO.41,409, flled- Jilly 8, A composition of sgid 823d 25 1925, for"Softeners for pyroxylins, in which m 7 mixed 0! P ed-nom celluloseester compositions containing .benzyl hydrocarbon 7 2211 fis y OM butylphthalate are claimed specifically. the n w which g 0 r: err

As many apparently wid ly diiferentembodland W er mm be 1 so so ments ofthis invention may be mad;1 g o m e mine new i the int and scope ereo mI g fi b e u ndxood 1 we do not limit ourselves A composition of mattercomprising nzrl to the specific embodiments thereof except as Phtmlate-4 v defined in the appended patent claims. EBENEZER. REID.

l. A composition of matter comprising a by- I Certificate of CorrectionPatent No. 1,984,283. v I

' EBENEZER EMMET REID ET AL.

It is hereby certified that errors appear in tHeIPrinted specificationof theabove December 11, 1934.

numbered patent re uu-i correction as follow age 1, second column, line37, for the period before 0O second occurrence insert a dash; age 3,first column,

e 48, strike out-last line of formula and insert instead (6 11030005 andpage 4, second column, line 2, claim 1, for the syllable boxlic readbozyl'ic; and that the said Letters Patent should be read with thesecorrections therein that the same may conform to the record of the casein the Patent Ofiice.

Signed andsealed this 5th day of March, A. B21935.

- I LESLIE FRAZER, Acting Commissioner qfPatente.

